CN107349947A - A kind of acetic acid hydrogenation catalyst and its application - Google Patents
A kind of acetic acid hydrogenation catalyst and its application Download PDFInfo
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- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
A kind of acetic acid hydrogenation catalyst provided by the invention, including active component and carrier, it is preferred that emphasis is also include the carbonate of one or both of calcium and barium.The generation of strong alkaline substance is avoided while reducing catalyst acid amount using calcium carbonate and barium carbonate in the present invention, and then catalyst surface solid alkali number is declined to a great extent, it is achieved thereby that acetic acid hydrogenation catalyst its alkali number while catalyst acid amount is reduced also does not improve, and then avoid the generation of accessory substance acetone, isopropanol.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of acetic acid hydrogenation catalyst and its application.
Background technology
Ethanol is a kind of important chemical industry, medicine, the energy and raw-food material.Acetic acid preparation of ethanol through hydrogenation is industrial at present
Prepare one of common method of ethanol.This method, which prepares ethanol, mainly includes two kinds of approach, first, acetic acid generates acetic acid through esterification
Ester, then acetate is hydrogenated to ethanol, then carries out refined raw producing and ethanol product;Second, acetic acid direct hydrogenation generates ethanol, then
Alcohol product is produced through subtractive process.No matter it is above-mentioned which kind of prepare ethanol during, can all produce substantial amounts of accessory substance such as first
Alkane, ethane, carbon monoxide, acetaldehyde, ether, ethyl acetate and acetone etc..And the catalyst used in hydrogenation process, can be effective
Reduction accessory substance generation, improve the yield of ethanol.Influenceing the catalytic performance of acetic acid hydrogenation catalyst mainly has two aspects,
First, the acidic site of catalyst surface, the bronsted acid position of catalyst surface can promote ethanol to be converted into ethyl acetate, drop
The yield of low ethanol, second, active component, it influences the catalytic activity of catalyst, the catalysis currently used for acetic acid preparation of ethanol by hydrogenating
The active component of agent is mostly noble metal, such as Pt, Ag, in the preparation of scale ethanol, frequently can lead to planning and cost
It is too high, and the surface acidity position of catalyst is not modified, so that existing acetic acid hydrogenation catalyst is in catalytic process
Poor selectivity.
In the prior art, a kind of methods with acetate preparation of ethanol through hydrogenation of Chinese patent literature CN102093162B,
The active component for disclosing the catalytic hydrogenation catalyst used is copper, and carrier is silica, and with transition metal or/and alkali gold
One or more in category are as auxiliary agent;And define source for silicate etc., and also define alkali metal for magnesium and
One kind in barium.Abandoned in above-mentioned catalyst and used noble metal to reduce the cost of catalyst, and make as active component
With the carrier of silicate, the acidic site of catalyst surface is decreased, but above-mentioned patent is reducing support surface acidity position
The alkalescence of carrier surface is improved simultaneously, but the increase of catalyst surface alkalescence can cause the amount of accessory substance acetone to increase
Add, and then reduce the yield of ethanol, while during caused by acetone, can also by-product carbon dioxide, cause recycle hydrogen
Inert gas in gas accumulates, and so as to need to discharge a part from circulating air, i.e., so-called periodic off-gases, this can cause to add
Hydrogen gas consumption increase during hydrogen, and acetone can be converted into isopropanol in hydrogen, but isopropanol and ethanol are due to boiling
Point is close, is very difficult to separation, can not often separate, and this has resulted in containing substantial amounts of isopropanol impurity in ethanol,
This point has related narration in patent CN102414150A, in turn results in the adverse effect to alcohol product property.
Acetone and isopropanol are the problem in acetic acid preparation of ethanol by hydrogenating, such as SalvadorAnd Enrique
(article is published in the catalysis meeting of North America in 2009 for the acetic acid gas phase hydrogenation reaction that Iglesia has investigated on the ruthenium-based catalyst of load
View), reaction condition is:150~350 DEG C of temperature, normal pressure;Acetone is one of main accessory substance, in extreme situations acetone
Selectivity can reach 40%.Author has also investigated acetic acid conversion situation during using pure carrier as catalyst, finds pure
Also there is the production of acetone on carrier, can reach 30% or so in the case of extreme;Author thinks that the generation of acetone is also due to
The surface alkalinty of catalyst causes.Therefore while catalyst surface acidity is reduced, it is also most important to reduce surface alkalinty
, but for now, people's concern is very few.
The content of the invention
Therefore, the technical problem to be solved in the present invention is to overcome is reducing the same of support surface acidity position in the prior art
When add carrier surface alkalescence, so as to cause accessory substance acetone, isopropanol amount increase, reduce ethanol yield and purity lack
Fall into, so as to provide a kind of acetic acid hydrogenation catalyst and its application.
A kind of acetic acid hydrogenation catalyst, including active component and carrier, in addition to regulation component, the regulation component is alkali
One or more in metal and/or alkaline earth metal carbonate.
Preferably, in described acetic acid hydrogenation catalyst, it is described regulation component be selected from calcium carbonate, potassium carbonate, magnesium carbonate,
One or more in sodium carbonate and barium carbonate.
Preferably, in described acetic acid hydrogenation catalyst, the regulation component is calcium carbonate and/or barium carbonate.
Preferably, in described acetic acid hydrogenation catalyst, the crystalline phase granularity of the carbonate is 2-20nm.
Preferably, in described acetic acid hydrogenation catalyst, the regulation component accounts for the total matter of acetic acid hydrogenation catalyst
The 0.5-8wt% of amount.
Preferably, in described acetic acid hydrogenation catalyst, described hydrogenation catalyst composition formula is ABC@S;
A and B is the active component, and C is the regulation component, and S is the carrier;
Wherein, the active component A is selected from the oxide of cobalt and/or copper;The active component B is selected from tin, tungsten, molybdenum and iron
Oxide in one or more;
The carrier S is selected from silica, zirconium oxide or activated carbon.
Preferably, in described acetic acid hydrogenation catalyst, the active component A, the active component B and the regulation
Component C mol ratio is:1:(0.5-1.1):(0.05-0.2).
Preferably, in described acetic acid hydrogenation catalyst, in terms of the gross mass of the acetic acid hydrogenation catalyst,
The content of the active component A is 15-30%;
The content of the active component B is 10-40%;
The content of the carrier S is 10-55%.
A kind of acetic acid hydrogenation catalyst of the present invention, the application in acetic acid preparation of ethanol through hydrogenation is catalyzed.
Technical solution of the present invention, have the following advantages that:
1. a kind of acetic acid hydrogenation catalyst provided by the invention, including active component and carrier, it is preferred that emphasis is also including calcium,
One or more of carbonate in potassium, magnesium, sodium and barium.Alkali carbonate and/or alkaline-earth metal carbonic acid are used in the present invention
Salt regulation reduces the acid amount of catalyst, while using the electron-withdrawing property being greatly reduced of carbonate, reduces the alkali of strong basicity
Metal and/or the amount of alkaline earth oxide generation, carry out so that base strength declines to a great extent, it is achieved thereby that acetic acid hydrogenation is urged
The agent effect that its alkali number does not also improve while catalyst acid amount is reduced, and then avoid due to catalyst alkali number mistake
Height, cause have the problem of accessory substance acetone, isopropanol generation.
2. a kind of acetic acid hydrogenation catalyst provided by the invention, selects the carbonate of suitable crystalline phase size, avoids
After carbonate crystalline phase size is more than 20nm, its load factor is influenceed, and then influences the ability to the acid regulation of catalyst surface.
Embodiment
Technical scheme will be clearly and completely described below, it is clear that described embodiment is this hair
Bright part of the embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art exist
The every other embodiment obtained under the premise of creative work is not made, belongs to the scope of protection of the invention.Under in addition,
As long as involved technical characteristic does not form conflict can phase each other in the different embodiments of the present invention described by face
Mutually combine.
Embodiment 1
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps:
(1) cobalt nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid tin, after stirring,
Obtain soak;
(2) sodium carbonate is added into the soak, forms precipitated liquid, silica is added into the precipitated liquid and is carried
Body, 3h is cured in the case where temperature is 80 DEG C of hydrothermal condition, was filtrated to get filter solid;
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 100 DEG C in temperature
After lower drying, in 300 DEG C of roastings, the catalyst precursor is obtained;
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 150kpa, control the temperature in reaction vessel to be in 50 DEG C, carbonization treatment 20h, that is, obtain the acetic acid that formula is ABC S and be hydrogenated with
Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of cobalt, the oxide of tin, iron
Thing, calcium carbonate and carrier silicas account for 15%, 20%, 10%, 3% and the 52% of acetic acid hydrogenation catalyst gross mass respectively.
Embodiment 2
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps:
(1) copper nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid molybdenum, after stirring,
Obtain soak;
(2) sodium carbonate is added into the soak, forms precipitated liquid, silica is added into the precipitated liquid and is carried
Body, 5h is cured in the case where temperature is 70 DEG C of hydrothermal condition, was filtrated to get filter solid;
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, in the case where temperature is 80 DEG C
After drying, in 600 DEG C of roastings, the catalyst precursor is obtained;
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 250kpa, control the temperature in reaction vessel to be in 70 DEG C, carbonization treatment 30h, that is, obtain the acetic acid that formula is ABC S and be hydrogenated with
Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of copper, the oxide of molybdenum, iron
Thing, calcium carbonate and carrier silicas account for 35%, 2%, 12% and the 4% and 47% of acetic acid hydrogenation catalyst gross mass respectively.
Embodiment 3
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps:
(1) copper nitrate and barium nitrate are added to the water, after stirring, add nitric acid tungsten and nitric acid molybdenum, after stirring,
Obtain soak;
(2) sodium carbonate is added into the soak, precipitated liquid is formed, Zirconia carrier is added into the precipitated liquid,
1h is cured in the case where temperature is 90 DEG C of hydrothermal condition, was filtrated to get filter solid;
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 150 DEG C in temperature
After lower drying, in 450 DEG C of roastings, the catalyst precursor is obtained;
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 200kpa, control the temperature in reaction vessel to be in 20 DEG C, carbonization treatment 12h, that is, obtain the acetic acid that formula is ABC S and be hydrogenated with
Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of copper, the oxide of molybdenum, tungsten
Thing, barium carbonate and carrier Zirconia carrier account for 20%, 10%, 30%, 0.5% and of acetic acid hydrogenation catalyst gross mass respectively
39.5%.
Embodiment 4
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps:
(1) cobalt nitrate and magnesium nitrate are added to the water, and after stirring, add nitric acid tin and ferric nitrate, after stirring, obtain
To soak;
(2) sodium carbonate is added into the soak, precipitated liquid is formed, absorbent charcoal carrier is added into the precipitated liquid,
5h is cured in the case where temperature is 80 DEG C of hydrothermal condition, was filtrated to get filter solid;
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 150 DEG C in temperature
After lower drying, in 500 DEG C of roastings, the catalyst precursor is obtained;
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 170kpa, control the temperature in reaction vessel to be in 100 DEG C, carbonization treatment 48h, that is, obtain the acetic acid that formula is ABC S and add
Hydrogen catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of cobalt, the oxide of tin, iron
Thing, magnesium carbonate and carrier active carbon account for 30%, 5%, 5% and the 8% and 52% of acetic acid hydrogenation catalyst gross mass respectively.
Embodiment 5
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps:
(1) cobalt nitrate and sodium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid tin, after stirring,
Obtain soak;
(2) sodium carbonate is added into the soak, forms precipitated liquid, silica is added into the precipitated liquid and is carried
Body, 3h is cured in the case where temperature is 80 DEG C of hydrothermal condition, was filtrated to get filter solid;
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, is 100 DEG C in temperature
After lower drying, in 500 DEG C of roastings, the catalyst precursor is obtained;
(4) catalyst precursor is placed in closed reaction vessel, is passed through carbon dioxide, until its partial pressure
For 220kpa, control the temperature in reaction vessel to be in 80 DEG C, carbonization treatment 30h, that is, obtain the acetic acid that formula is ABC S and be hydrogenated with
Catalyst.
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of cobalt, the oxide of tin, iron
Thing, sodium carbonate and carrier silicas account for 15%, 20%, 10% and the 3% and 52% of acetic acid hydrogenation catalyst gross mass respectively.
Comparative example 1
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps:
(1) copper nitrate and calcium nitrate are added to the water, after stirring, add ferric nitrate and nitric acid molybdenum, after stirring,
Obtain soak;
(2) sodium carbonate is added into the soak, forms precipitated liquid, silica is added into the precipitated liquid and is carried
Body, 5h is cured in the case where temperature is 70 DEG C of hydrothermal condition, was filtrated to get filter solid;
(3) amount for cleaning filter solid to sodium carbonate thereon is less than the 2% of filtering solid masses, in the case where temperature is 80 DEG C
After drying, in 600 DEG C of roastings, acetic acid hydrogenation catalyst is obtained;
Wherein, in the acetic acid hydrogenation catalyst prepared in the present embodiment, the oxidation of the oxide of copper, the oxide of molybdenum, iron
Thing, the oxide of calcium and carrier silicas account for 35%, 2%, 12% and 4% and of acetic acid hydrogenation catalyst gross mass respectively
47%.
Comparative example 2
A kind of preparation method of acetic acid hydrogenation catalyst is present embodiments provided, is comprised the following steps:
10wt% cobalts and 1wt% chromium are prepared on graphite.
The uniform particle size with about 0.2mm through being milled and sieving is distributed at 120 DEG C in a nitrogen atmosphere in an oven
Graphite dry the whole night, is cooled to room temperature.Chromic nitrate nonahydrate, the solution in distilled water are added thereto.Will be resulting
Slurries are dried in 110 DEG C of baking oven is progressively heated at.Then the catalyst mixture through dipping is calcined at 500 DEG C (6h, 1
℃/min).Solution of the Cobalt(II) nitrate hexahydrate in distilled water is added into the material through calcining and cooling down.Will be resulting
Slurries are progressively heated in 110 DEG C of baking oven and dried, then calcine the catalyst mixture through dipping at 500 DEG C (6h, 1 DEG C/
min)。
Compliance test result
1. the effect of acetic acid hydrogenation catalyst prepared by couple embodiment 1-5 and comparative example 1-2 detects, testing result
It is shown in Table 1.
Testing conditions:220-230 DEG C, hydracid compares 30-50;Liquid hourly space velocity (LHSV) 0.4-0.8;
Table 1
2. acetic acid hydrogenation catalyst surface alkali number and acid amount prepared by couple embodiment 1-5 and comparative example 1-2 detect,
Testing result is shown in Table 2.
Surface acidity assay method:
Surface acidity uses temperature programmed desorption ammonia (NH3- TPD) method, in Micromeritics Auto
Carried out on Chem.2920 (USA), catalyst sample (150mg) is pre-processed into 3h for 350 DEG C in Ar streams first, is then cooled to
50 DEG C, it is passed through NH3Adsorb 30min, in Ar purging to baseline it is steady after start to warm up to 600 DEG C desorption ammonia (heating rates
10 DEG C/min), one is done to each catalyst and does not adsorb NH3Blank roasting experiment.Containing for 0.5ml is entered using pulse
5vol% NH3-Ar gaseous mixtures are demarcated to thermal conductivity cell detector (TCD) to be measured with gauging surface acid.
Surface alkali number measure method:
Surface alkali number uses temperature programmed desorption ammonia (CO2- TPD) method, in Micromeritics Auto
Carried out on Chem.2920 (USA), catalyst sample (150mg) is pre-processed into 3h for 350 DEG C in He streams first, is then cooled to
50 DEG C, it is passed through CO2Adsorb 30min, in He purging to baseline it is steady after start to warm up to 600 DEG C desorption CO2(heating rate 10
DEG C/min), a not CO absorption is done to each catalyst2Blank roasting experiment.Containing for 0.5ml is entered using pulse
5vol% CO2-He gaseous mixtures are demarcated with gauging surface alkali number to thermal conductivity cell detector (TCD).
Table 2
3. the crystal grain chi of the regulation component loaded on the acetic acid hydrogenation catalyst prepared with x-ray diffractometer embodiment 1-3
Little progress row detects, and is calculated according to ScheHer formula, and testing result is shown in Table 3.
Table 3
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (9)
1. a kind of acetic acid hydrogenation catalyst, including active component and carrier, it is characterised in that also include regulation component, the tune
It is the one or more in alkali metal and/or alkaline earth metal carbonate to save component.
2. acetic acid hydrogenation catalyst according to claim 1, it is characterised in that the regulation component is selected from calcium carbonate, carbon
One or more in sour potassium, magnesium carbonate, sodium carbonate and barium carbonate.
3. acetic acid hydrogenation catalyst according to claim 1 or 2, it is characterised in that it is described regulation component be calcium carbonate and/
Or barium carbonate.
4. according to any described acetic acid hydrogenation catalysts of claim 1-3, it is characterised in that the crystallite dimension of the carbonate
For 2-20nm.
5. according to any described acetic acid hydrogenation catalysts of claim 1-4, it is characterised in that the regulation component accounts for the vinegar
The 0.5-8wt% of sour hydrogenation catalyst gross mass.
6. according to any described acetic acid hydrogenation catalysts of claim 1-5, it is characterised in that described hydrogenation catalyst composition
Formula is ABC@S;
A and B is the active component, and C is the regulation component, and S is the carrier;
Wherein, the active component A is selected from the oxide of cobalt and/or copper;The active component B is selected from the oxygen of tin, tungsten, molybdenum and iron
One or more in compound;
The carrier S is selected from silica, zirconium oxide or activated carbon.
7. according to any described acetic acid hydrogenation catalysts of claim 1-6, it is characterised in that the active component A, the work
Property the component B and regulation component C mol ratio be:1:(0.5-1.1):(0.05-0.2).
8. the acetic acid hydrogenation catalyst according to claim 6 or 7, it is characterised in that with the acetic acid hydrogenation catalyst
Gross mass meter,
The content of the active component A is 15-30%;
The content of the active component B is 10-40%;
The content of the carrier S is 10-55%.
9. the acetic acid hydrogenation catalyst described in a kind of any one of claim 1-8, answering in acetic acid preparation of ethanol through hydrogenation is catalyzed
With.
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CN108358752A (en) * | 2018-04-18 | 2018-08-03 | 肖锦 | A kind of method of acetic acid hydrogenation ethyl alcohol |
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Cited By (1)
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CN108358752A (en) * | 2018-04-18 | 2018-08-03 | 肖锦 | A kind of method of acetic acid hydrogenation ethyl alcohol |
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